CN112236506A

CN112236506A - Cyclopentanone compounds

Info

Publication number: CN112236506A
Application number: CN201980037815.8A
Authority: CN
Inventors: J·库仑; E·德莫尔
Original assignee: Firmenich SA
Current assignee: Firmenich SA
Priority date: 2018-10-15
Filing date: 2019-10-14
Publication date: 2021-01-15
Also published as: IL278774B; MX2020012829A; WO2020078892A1; EP3775119B1; ES2914874T3; US20210230503A1; US11859151B2; IL278774A; JP2022502518A; EP3775119A1; US20240067895A1; JP7317867B2

Abstract

The present invention relates to the use as perfuming ingredient of a cyclopentanone compound of formula (I), for example to impart fruity, fruity-exotic types of odor notes:

Description

Cyclopentanone compounds

Technical Field

The invention relates to the field of spices (daily chemical essence). More particularly, it relates to the use of cyclopentanone compounds as perfuming ingredients. The present invention relates to the use of said compounds in the perfumery industry as well as to compositions or articles containing said compounds.

Background

To the best of our knowledge, none of the compounds of the present invention is known as a perfuming compound or a compound with a general odor.

Certain compounds of the invention may be known per se, but are only exemplified as chemical intermediates, for example J.Am.chem.Soc.,1994,116,4183-4188, J.Org.chem.,1994,59,3186-3192, Biocatalysis,1994,10,289-294 or Chemistry Letters,1984, 869-870.

However, these prior art documents do not report or suggest any organoleptic properties of the compounds of formula (I), or any use of said compounds in the field of perfumery.

Disclosure of Invention

The present invention relates to compounds of formula (I) which impart fruity-exotic (fruity-exotic) notes without floral nuances (aspect).

A first object of the present invention is therefore the use as perfuming ingredient of a compound of formula (I):

the compound is in the form of any one of its stereoisomers or mixtures thereof, and wherein n represents 1 or 2.

A second object of the present invention is a method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least one compound of formula (I):

A third object of the present invention is a perfuming composition comprising:

i) at least one compound of formula (I) as defined above;

ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and

iii) optionally, at least one flavor adjuvant.

Another object of the present invention is a perfumed consumer product comprising at least one compound of formula (I) as defined above or a composition as defined above.

Detailed Description

Surprisingly, it has now been found that the compounds of formula (I) can be used as perfuming ingredients, for example to impart fruity, fruity-exotic types of odor notes:

the compound is in the form of any one of its stereoisomers or a mixture thereof, wherein

n represents 1 or 2.

For the sake of clarity, the expression "any one of its stereoisomers or mixtures thereof" or similar terms is used to indicate the normal meaning understood by a person skilled in the art, i.e. the compounds of the invention may be pure enantiomers, or in the form of mixtures of enantiomers.

According to a particular embodiment of the invention, n represents 1.

According to a particular embodiment of the invention, the compound of formula (I) is 2- (hex-5-en-1-yl) cyclopent-1-one.

As specific examples of compounds of the invention, mention may be made, as non-limiting examples, of 2- (hex-5-en-1-yl) cyclopent-1-one, which has a fruito-lactone-exotic flavour, a mango-and passion fruit-like olfactory connotation.

When the odor of the compounds of the invention is compared with that of the prior art compound 2-pentylcyclopent-1-one, then the compounds of the invention differ from it by a significantly stronger fruity-exotic note and lack of floral-jasmine notes (characteristic of the prior art compounds).

Said differences make the compounds of the invention suitable for different uses, i.e. to impart different sensory impressions, respectively, to the prior art compounds.

As mentioned above, the present invention relates to the use of compounds of formula (I) as perfuming ingredients. In other words, it relates to a method or a process for imparting, enhancing, improving or modifying the odor properties of a perfuming composition or of a perfumed article or surface, which method comprises adding to said composition or article an effective amount of at least one compound of formula (I), for example to impart a typical note thereto. It will be appreciated that the final hedonic effect may depend on the precise dosage and organoleptic properties of the compounds of the invention, but that the addition of the compounds of the invention will impart a typical style in the form of a note (note), a style (touch) or a subtle feature (aspect) to the final product depending on the dosage.

By "use of a compound of formula (I)" it must be understood here also the use of any composition containing a compound of formula (I) and which can be advantageously used in the perfumery industry.

Said compositions, which in fact can be advantageously used as perfuming ingredients, are also objects of the present invention.

Therefore, another object of the present invention is a perfuming composition comprising:

i) at least one compound of the invention as defined above as perfuming ingredient;

iii) optionally, at least one flavor adjuvant.

By "perfumery carrier" is meant a material which is practically neutral from a perfumery point of view, i.e. does not significantly modify the organoleptic properties of perfuming ingredients. The carrier may be a liquid or a solid.

As liquid carrier there may be mentioned, as non-limiting examples, emulsifying systems, i.e. solvent and surfactant systems, or solvents commonly used in perfumery. A detailed description of the nature and type of solvents commonly used in perfumery is not exhaustive. However, mention may be made, as non-limiting examples, of solvents such as butanediol or propylene glycol, glycerol, dipropylene glycol and its monoethers, 1,2, 3-propanetriester triacetate, dimethyl glutarate, dimethyl adipate, 1, 3-diacetoxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2- (2-ethanediol), glycerol, dipropylene glycol and its monoethers, dimethyl glutarate, dimethyl adipate, 1, 3-diacetoxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, and the likeOxyethoxy) -1-ethanol, triethyl citrate or mixtures thereof, which are most commonly used. For compositions comprising both a fragrance carrier and a fragrance base, other suitable fragrance carriers than those specified above may also be ethanol, water/ethanol mixtures, limonene or other terpenes, isoparaffins, such as those under the trademark Iso-paraffins

Those known per se (source: Exxon Chemical), or glycol ethers and glycol ether esters, e.g. under the trade mark

Those known per se (source: Dow Chemical Company), or hydrogenated castor oil, for example under the trade mark

RH 40 (source: BASF).

By solid carrier is meant a material, to which a perfuming composition or some of the ingredients of a perfuming composition can be chemically or physically associated. Typically, such solid carriers are used to stabilize the composition, or to control the evaporation rate of the composition or certain ingredients. Solid carriers are currently used in the art, and the skilled person knows how to achieve the desired effect. However, as non-limiting examples of solid carriers there may be mentioned absorbent gums or polymers or inorganic materials, such as porous polymers, cyclodextrins, wood-based materials, organic or inorganic gels, clays, gypsum, talc or zeolites.

As other non-limiting examples of solid carriers, encapsulating materials may be cited. Examples of such materials may include wall-forming materials and plasticizing materials, such as monosaccharides, disaccharides or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinyl alcohols, proteins or pectins, or as described in references such as H.Scherz, Hydrokolloides: Stabilisatoren, Dickungs-und Geliermentil in Lebensemitel, Band 2 der Schrienreihe Lebensmittemel,

Behr's Verlag GmbH&materials listed in cobalt, Hamburg, 1996. Encapsulation is a process well known to those skilled in the art and can be carried out, for example, using techniques such as spray drying, agglomeration or extrusion; or consist of coating encapsulation including coacervation and complex coacervation techniques.

As non-limiting examples of solid carriers, mention may be made in particular of core-shell capsules using resins of the aminoplast, polyamide, polyester, polyurea or polyurethane type or mixtures thereof, all of which are well known to those skilled in the art, by phase separation processes initiated by the use of polymerization, interfacial polymerization, coacervation, and the like techniques or these techniques together, all of which have been described in the prior art, and optionally in the presence of polymeric stabilizers or cationic copolymers.

The resins may be produced by the polycondensation of aldehydes (such as formaldehyde, 2-dimethoxyacetaldehyde, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof) with amines such as urea, benzoguanamine, glycoureido, melamine, methylolmelamine, methylated methylolmelamine, guanazol and the like and mixtures thereof. Alternatively, preformed resin alkylated polyamines may be used, for example under the trademark Acrylolated

(Source: Cytec Technology Corp.), Cy

(source: Cytec Technology Corp.),

Or

(source: BASF) commercially available.

Other resins are prepared by reacting a polyol such as glycerol with a polyisocyanate such as a trimer of hexamethylene diisocyanate, isophorone diisocyanate or xylylene diisocyanateTrimer of acid ester or biuret of hexamethylene diisocyanate, or trimer of xylylene diisocyanate and trimethylolpropane (trade name)

Known, sources: mitsui Chemicals), among which the biuret of xylylene diisocyanate with the trimer of trimethylolpropane and hexamethylene diisocyanate is preferred.

Some research literature relating to the encapsulation of fragrances by polycondensation of amino resins, i.e. melamine-based resins, with aldehydes includes articles such as Acta Polymerica,1989, vol.40, pages 243,325 and 683 and 1990, vol.41, page 91, published by k. These articles have described various parameters affecting the preparation of such core-shell microcapsules according to prior art processes, which are also further detailed and exemplified in the patent literature. US 4'396'670 to Wiggins Teape Group Limited is a related early example of the latter. Since then, many other authors have enriched the literature in this area, and it is not possible here to cover all published developments, but the general knowledge of encapsulation techniques is of great importance. More recent targeted publications also relate to suitable uses of such microcapsules, and are represented by articles such as K.Bruyninckx and M.Dusselier, ACS Sustainable Chemistry & Engineering,2019, vol.7, pages 8041-.

By "perfumery base" is meant here a composition comprising at least one perfuming co-ingredient.

Said perfuming co-ingredient is not of formula (I). By "perfuming co-ingredient", it is moreover meant a compound, which is used in a perfuming preparation or composition to impart a hedonic effect. In other words, such a co-ingredient to be considered as being a perfuming co-ingredient must be recognized by a person skilled in the art as being capable of imparting or modifying in an active or pleasant way the odor of a composition, and not just as having an odor.

The nature and type of the perfuming co-ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the intended use or application and the desired organoleptic effect. In general, these perfuming co-ingredients belong to different chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and can be of natural or synthetic origin.

Mention may in particular be made of perfuming co-ingredients known to have a smell-like note, such as:

mention may in particular be made of the perfuming co-ingredients commonly used in perfumery formulations, such as:

-aldehyde fragrance component: decanal, dodecanal, 2-methylundecanal, 10-undecenal, octanal and/or nonenal;

-aromatic herbal ingredients: eucalyptus oil, camphor, eucalyptol, 5-methyl tricyclo [ 6.2.1.0-2, 7- ] undec-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4, 4-dimethyl-1, 3-oxathiane (oxathiane), 2,2,7/8, 9/10-tetramethyl spiro [5.5] undec-8-en-1-one, menthol and/or alpha-pinene;

-a balm component: coumarin, ethyl vanillin and/or vanillin;

-citrus flavour components: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, auraptene, limonene, 1-p-menthen-8-yl acetate and/or 1,4(8) -p-menthadiene;

-floral composition: methyl dihydrojasmonate, linalool, citronellol, phenethyl alcohol, 3- (4-tert-butylphenyl) -2-methylpropionaldehyde, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4 (2H) -pyranol, β -ionone, methyl 2- (methylamino) benzoate, (E) -3-methyl-4- (2,6, 6-trimethyl-2-cyclohexen-1-yl) -3-buten-2-one, (1E) -1- (2,6, 6-trimethyl-2-cyclohexen-1-yl) -1-penten-3-one, 1- (2,6, 6-trimethyl-1, 3-cyclohexadien-1-yl) -2-buten-1-one, (2E) -1- (2,6, 6-trimethyl-2-cyclohexen-1-yl) -2-buten-1-one, (2E) -1- [2,6, 6-trimethyl-3-cyclohexen-1-yl ] -2-buten-1-one, (2E) -1- (2,6, 6-trimethyl-1-cyclohexen-1-yl) -2-buten-1-one, 2, 5-dimethyl-2-indanol, 2,6, 6-trimethyl-3-cyclohexen-1-carboxylate, methyl tert-butyl acetate, ethyl, 3- (4, 4-dimethyl-1-cyclohexen-1-ylpropanal, hexyl salicylate, 3, 7-dimethyl-1, 6-nonadien-3-ol, 3- (4-isopropylphenyl) -2-methylpropanal, tricyclodecenyl acetate, geraniol, p-menth-1-en-8-ol, 4- (1, 1-dimethylethyl) -1-cyclohexyl acetate, 1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, pentyl salicylate, homocis-dihydrojasmonic acid methyl ester, 3-methyl-5-phenyl-1-pentanol, tricyclodecenyl propionate, methyl salicylate, methyl propionate, methyl, Geranyl acetate, tetrahydrolinalool, cis-7-p-menthol, propyl (S) -2- (1, 1-dimethylpropoxy) propionate, 2-methoxynaphthalene, 2,2, 2-trichloro-1-phenylethyl acetate, 4/3- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbaldehyde, amyl cinnamaldehyde, 8-decene-5-lactone, 4-phenyl-2-butanone, isononyl acetate, 4- (1, 1-dimethylethyl) -1-cyclohexyl acetate, tricyclodecenyl isobutyrate and/or a mixture of methylionone isomers;

-fruit aroma components: gamma-undecalactone, 2, 5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1, 3-oxathiane, 4-decalactone, ethyl 2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1, 3-dioxolane-2-acetate, 3- (3,3/1, 1-dimethyl-5-indanyl) propanal, diethyl 1, 4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, [ 3-ethyl-2-oxiranyl ] acetic acid 1- [3, 3-dimethylcyclohexyl ] ethyl ester and/or diethyl 1, 4-cyclohexanedicarboxylate;

-green components: 2-methyl-3-hexanone (E) -oxime, 2, 4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styryl acetate, allyl (2-methylbutoxy) acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z) -3-hexen-1-ol and/or 1- (5, 5-dimethyl-1-cyclohexen-1-yl) -4-penten-1-one;

-a musk component: 1, 4-dioxa-5, 17-cyclopentadecanedione, (Z) -4-cyclopentadecen-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecen-2-one, 1-oxa-13-cyclohexadecen-2-one, (9Z) -9-cyclopentadecen-1-one, 2- {1S) -1- [ (1R) -3, 3-dimethylcyclohexyl ] ethoxy } -2-oxoethyl propionate, 3-methyl-5-cyclopentadecene-1-one, 1,3,4,6,7, 8-hexahydro-4, 6,6,7,8, 8-hexamethylcyclopenta [ G ] -2-benzopyran, (1S,1'R) -2- [1- (3',3 '-dimethyl-1' -cyclohexyl) ethoxy ] -2-methylpropyl propionate, oxacyclohexadecan-2-one and/or (1S,1'R) - [1- (3',3 '-dimethyl-1' -cyclohexyl) ethoxycarbonyl ] methyl propionate;

-a woody component: 1- [ (1RS,6SR) -2,2, 6-trimethylcyclohexyl]-3-hexanol, 3-dimethyl-5- [ (1R) -2,2, 3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4 '-dimethylspiro [ ethylene oxide-2, 9' -tricyclo [6.2.1.0 ]^2,7]Eleven carbon [ 4]]Alkene, (1-ethoxyethoxy) cyclododecane, acetic acid 2,2,9, 11-tetramethylspiro [5.5]]Undec-8-en-1-yl ester, 1- (octahydro-2, 3,8, 8-tetramethyl-2-naphthyl) -1-ethanone, patchouli oil, terpene fractions of patchouli oil,

(1'R, E) -2-ethyl-4- (2',2',3' -trimethyl-3 '-cyclopenten-1' -yl) -2-buten-1-ol, 2-ethyl-4- (2,2, 3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, methyl cedryl ketone, 5- (2,2, 3-trimethyl-3-cyclopentenyl) -3-methylpentan-2-ol, 1- (2,3,8, 8-tetramethyl-1, 2,3,4,6,7,8,8 a-octahydronaphthalen-2-yl) ethan-1-one and/or isobornyl acetate;

other ingredients (e.g. amber, pink, spicy or watery): dodecahydro-3 a,6,6,9 a-tetramethylnaphtho [2,1-b ] furan and any of its stereoisomers, piperonal, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3- (1, 3-benzodioxol-5-yl) -2-methylpropanal, 7-methyl-2H-1, 5-benzodioxepin-3 (4H) -one, 2,5, 5-trimethyl-1, 2,3,4,4a,5,6, 7-octahydro-2-naphthol, 1-phenyl vinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro [4.4] nonane and/or 3- (3-isopropyl-1-phenyl) butyraldehyde.

The perfumery base according to the invention may not be limited to the perfuming co-ingredients mentioned above, and many other such co-ingredients are in any case listed in the literature references, such as s.arctander, Perfume and Flavor Chemicals,1969, montcalair, New Jersey, USA or a newer version thereof, or other works of similar nature, as well as a large number of patent documents in the field of perfumery. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming compounds, also known as pro-fragrances (perfume) or pro-fragrances (perfragrance). Non-limiting examples of suitable pro-fragrances may include 4- (dodecylthio) -4- (2,6, 6-trimethyl-2-cyclohexen-1-yl) -2-butanone, 4- (dodecylthio) -4- (2,6, 6-trimethyl-1-cyclohexen-1-yl) -2-butanone, trans-3- (dodecylthio) -1- (2,6, 6-trimethyl-3-cyclohexen-1-yl) -1-butanone, 2-phenylethyl oxo (phenyl) acetate or mixtures thereof.

By "perfumery adjuvant" we mean here an ingredient capable of imparting additional benefits such as colour, specific light fastness, chemical stability, etc. A detailed description of the nature and type of adjuvants commonly used in perfuming compositions is not exhaustive, but it must be mentioned that said ingredients are well known to the person skilled in the art. Specific non-limiting examples may be listed as follows: viscosity agents (e.g., surfactants, thickeners, gelling and/or rheology modifiers), stabilizers (e.g., preservatives, antioxidants, heat/light or buffering agents or chelating agents, such as BHT), colorants (e.g., dyes and/or pigments), preservatives (e.g., antibacterial or antimicrobial agents or antifungal or anti-irritant agents), abrasives, skin cooling agents, fixatives, insect repellents, ointments, vitamins, and mixtures thereof.

It is understood that the person skilled in the art is fully capable of designing optimal formulations for the desired effect, simply by applying the standard knowledge in the field and by mixing the above-mentioned components of the perfuming composition by trial and error.

In addition to perfuming compositions comprising at least one compound of formula (I), at least one perfumery carrier, at least one perfumery base and optionally at least one perfumery adjuvant, perfuming compositions consisting of at least one compound of formula (I) and at least one perfumery carrier also constitute a particular embodiment of the invention.

According to a particular embodiment, the above composition comprises more than one compound of formula (I), which enables the perfumer to prepare accords or fragrances having the odor profile of the different compounds of the invention, creating new building blocks for the purpose of creation.

For the sake of clarity, it is also understood that any mixture directly resulting from chemical synthesis (wherein the composition of matter of the invention acts as starting material, intermediate or end product), for example a reaction medium which is not sufficiently purified, cannot be considered as a perfuming composition according to the invention, provided that said mixture does not provide the compound of the invention in a suitable form for perfumery. Thus, unpurified reaction mixtures are generally excluded from the present invention unless otherwise specified.

The compounds of the invention can also be advantageously used in all fields of modern perfumery, i.e. fine perfumery or functional perfumery, to actively impart or modify the odor of a consumer product to which said compounds of formula (I) are added. Therefore, another object of the present invention is a perfumed consumer product comprising, as perfuming ingredient, at least one compound of formula (I) as defined above.

The compounds of the invention can be added as such or as part of the perfuming compositions of the invention.

For the sake of clarity, "perfumed consumer product" means a consumer product which delivers at least one pleasant perfuming effect to the surface or space to which it is applied, e.g. skin, hair, fabric or household surface. In other words, a perfumed consumer product according to the invention is a perfumed consumer product comprising the functional formulation and optionally additional benefit agents corresponding to the desired consumer product, and an olfactory effective amount of at least one compound of the invention. For the sake of clarity, said perfumed consumer product is a non-edible product.

The nature and type of the ingredients of perfumed consumer product do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the nature and the desired effect of said product.

Non-limiting examples of suitable perfumed consumer products include perfumes, such as fine perfumes, spread perfumes (splash) or light perfumes (eau de perfume), colognes or shave or after-shave lotions; fabric care products such as liquid or solid detergents, fabric softeners, liquid or solid fragrance enhancers, fabric refreshers, ironing waters, papers, bleaches, carpet cleaners, curtain care products; body care products, such as hair care products (e.g., shampoos, colorants or hair sprays, color care products, hair styling products, dental care products), disinfectants, personal care products; cosmetic preparations (e.g. skin creams or lotions, vanishing creams, body deodorants or antiperspirants (e.g. sprays or roll-ons), depilatories, tanning agents, sun-or after-sun products, nail products, skin cleansing products, cosmetics); or a skin care product (e.g. a soap, bath mousse, oil or gel, or a hygiene product or foot/hand care product); air care products such as air fresheners or "ready-to-use" powder air fresheners, which can be used in home spaces (rooms, refrigerators, cabinets, shoes or cars) and/or public spaces (halls, hotels, malls, etc.); or a home care product, such as a mould remover, a furniture care product, a wipe, a dishwashing detergent or a hard surface (e.g. floor, bathroom, sanitaryware or window cleaning) detergent; leather care products; automotive care products such as polishes, waxes or plastic cleaners.

Some of the above mentioned perfumed consumer products may represent an aggressive medium for the compounds of the invention and may therefore need to be protected from premature decomposition, e.g. by encapsulation or by chemically binding them to another chemical substance suitable for releasing the ingredients of the invention upon exposure to a suitable external stimulus, such as an enzyme, light, heat or a change in pH.

The proportions in which the compounds according to the invention can be incorporated in the various aforementioned products or compositions vary within a wide range of values. When the compounds according to the invention are mixed with perfuming co-ingredients, solvents or additives commonly used in the art, these values depend on the nature of the article to be perfumed and on the desired organoleptic effect as well as on the nature of the co-ingredients in a given base.

For example, in the case of perfuming compositions, typical concentrations are in the range of from 0.001% to 10% by weight, or even more, of the compound of the invention based on the weight of the composition into which it is incorporated. In the case of perfumed consumer products, typical concentrations of the compounds of the invention are in the range of from 0.001 wt% to 5 wt%, or even more, based on the total weight of the consumer product into which they are incorporated.

The compounds of the invention may be prepared according to standard procedures known in the art as described below.

Examples

The invention will now be described in more detail by the following examples, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees Celsius (. degree. C.); NMR spectroscopic data on¹H and¹³c in CDCl with a machine of 360MHz or 400MHz₃Chemical shifts δ are expressed in ppm relative to TMS as standard and coupling constants J are expressed in Hz, recorded in (if not otherwise stated).

Example 1

Synthesis of Compounds of formula (I)

2- (hex-5-en-1-yl) cyclopent-1-one

Step 1: 1- (hex-5-en-1-yl) -2-oxocyclopentane-1-carboxylic acid ethyl ester:

to a solution of ethyl 2-oxocyclopentane-1-carboxylate (56mL, 375mmol, 1 eq) in acetone (871mL) was added potassium carbonate (118g, 845mmol, 2.25 eq) and potassium iodide (20g, 120mmol, 0.32 eq) rapidly at room temperature. After stirring for 10 min, a solution of 6-bromohex-1-ene (51mL, 381mmol, 1.01 equiv.) in acetone (232mL) was added and the reaction refluxed for 19 h. Diethyl ether (900mL) was added, the mixture was filtered over a pad of celite, and the solvent was evaporated. The residue was diluted with ether, washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo to give ethyl 1- (hex-5-en-1-yl) -2-oxocyclopentane-1-carboxylate as an oil (93.3g, 91% purity, 95% yield).

¹H NMR:1.25(t,J＝7.1Hz,3H),1.27-1.42(m,4H),1.53-1.59(m,1H),1.86-2.07(m,6H),2.21-2.28(m,1H),2.37-2.44(m,1H),2.50-2.56(m,1H),4.11-4.21(m,2H),4.92-5.01(m,2H),5.73-5.82(m,1H).

¹³C NMR:215.0(s),171.1(s),138.6(d),114.5(t),61.3(t),60.5(s),38.0(t),33.7(t),33.4(t),32.7(t),29.1(t),24.3(t),19.6(t),14.1(q).

Step 2: 2- (hex-5-en-1-yl) cyclopent-1-one:

to a solution of the ketoester of step 1 (93.3g, 91% purity, 356mmol, 1 equiv) in methanol (860mL) at room temperature was added dropwise 6M aqueous HCl (428mL, 2.57mol, 7.2 equiv). The reaction was refluxed for 6 days. Diethyl ether was added and the aqueous layer was extracted twice with diethyl ether. The combined organic extracts were washed successively with water, saturated sodium bicarbonate solution, water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by distillation on a Vigreux column (92-93 ℃ C., 1.5mbar) to give the desired ketone as an oil (42.0g, 71% yield).

¹H NMR:1.21-1.44(m,5H),1.46-1.56(m,1H),1.71-1.83(m,2H),1.96-2.15(m,5H),2.18-2.33(m,2H),4.91-5.02(m,2H),5.74-5.85(m,1H).

¹³C NMR:221.5(s),138.9(d),114.4(t),49.1(d),38.2(t),33.6(t),29.6(t),29.5(t),28.9(t),27.0(t),20.8(t).

2- (hept-6-en-1-yl) cyclopent-1-one

Step 1: 1- (hept-6-en-1-yl) -2-oxocyclopentane-1-carboxylic acid ethyl ester:

to a solution of ethyl 2-oxocyclopentane-1-carboxylate (3.56mL, 26.7mmol, 1 eq) in acetone (62mL) was added potassium carbonate (8.43g, 60.4mmol, 2.25 eq) and potassium iodide (1.43g, 8.55mmol, 0.32 eq) rapidly at room temperature. After stirring for 10 min, a solution of 7-bromohept-1-ene (4.23mL, 26.9mmol, 1.01 equiv.) in acetone (17mL) was added and the reaction refluxed for 23 h. Diethyl ether (100mL) was added, the mixture was filtered over a pad of celite, and the solvent was evaporated. The residue was diluted with ether, washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo to give 1- (hept-6-en-1-yl) -2-oxocyclopentane-1-carboxylic acid ethyl ester as an oil (6.37g, 88% purity, 92% yield).

Step 2: 2- (hept-6-en-1-yl) cyclopent-1-one:

to a solution of the ketoester of step 1 (6.64g, 88% purity, 24.5mmol, 1 equiv) in methanol (59mL) was added dropwise 6M aqueous HCl (29.4mL, 177mol, 7.2 equiv) at room temperature. The reaction was refluxed for 5 days. Diethyl ether was added and the aqueous layer was extracted twice with diethyl ether. The combined organic extracts were washed successively with water, saturated sodium bicarbonate solution, water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel (heptane/AcOEt 95:5) and subjected to ball-to-ball distillation (115 ℃ C., 0.8-0.9 mbar) to give the desired ketone as an oil (3.06g, 68% yield).

¹H NMR(CDCl₃,400MHz):1.22-1.41(m,7H),1.48-1.55(m,1H),1.73-1.81(m,2H),1.97-2.13(m,5H),2.19-2.23(s,1H),2.27-2.31(m,1H),4.95-5.00(m,2H),5.76-5.83(m,1H).

¹³C NMR(CDCl₃,100MHz):221.6(s),139.0(d),114.3(t),49.1(d),38.2(t),33.7(t),29.7(t),29.6(t),29.1(t),28.7(t),27.4(t),20.8(t).

Example 2

Preparation of perfuming compositions

A perfuming composition was prepared by mixing the following ingredients:

in dipropylene glycol

1) Pentadecenyl lactone; the source is as follows: switzerland Geneva Firmenich SA

2) Methyl dihydrojasmonate; the source is as follows: switzerland Geneva Firmenich SA

3) (1S,1'R) -2- [1- (3',3 '-dimethyl-1' -cyclohexyl) ethoxy ] -2-methylpropyl propionate; the source is as follows: switzerland Geneva Firmenich SA

4) 2-tert-butyl-1-cyclohexyl acetate; the source is as follows: international Flavors & Fragrances of the United states

To the above composition, 80 parts by weight of 2- (hex-5-en-1-yl) cyclopent-1-one are added, giving the latter a fruity-exotic (mango and passion fruit-like) connotation with a small amount of acid nuance (facet), making the aroma more juicy and natural.

When 2-heptylcyclopent-1-one (fleuram one, jasmone) was added instead of the compound of the present invention, almost no effect was observed in the above composition. The above composition becomes slightly flowery (jasmine-like).

When 2-pentylcyclopent-1-one (Delphone) is added in place of the compounds of the present invention, the perfume composition becomes more green (like celery) and more floral (like jasmine).

Example 3

Preparation of liquid detergents containing the Compounds of the invention

Table 1: composition of liquid detergent formulation

1) Hostapur SAS 60; the source is as follows: clariant

2) Edenor K12-18; the source is as follows: cognis

3) Genapol LA 070; the source is as follows: clariant

4) The source is as follows: genencor International

5) Aculyn 88; the source is as follows: dow Chemical

Liquid detergents were prepared by adding 1.5 wt% of the composition of the invention of example 2 to the unperfumed liquid detergent formulation of table 1 under gentle shaking.

Example 4

Preparation of Fabric softeners comprising the Compound of the invention

Table 2: composition of softening agent formula

Composition (I)	Concentration [ weight%]
		Methyl bis [ tallowate ethyl ester group]Ammonium methyl (2-hydroxyethyl) sulfate¹⁾	12.20
1, 2-benzisothiazolin-3-ones²⁾	0.04
		CaCl₂(10% aqueous solution)	0.40
Water (W)	87.36

1) Stepandex VL 90A Diester Quat; the source is as follows: stepan

2) Proxel GXL; the source is as follows: arch

Methyl bis [ tallowate ethyl ester ] heated to 65 ℃ by weighing]-2-hydroxyethyl ammonium methyl sulfate to prepare the softener. Then water and 1, 2-benzisothiazolin-3-one are placed in a reactor and heated at 65 ℃ with stirring. To the above mixture was added methyl bis [ tallowate ethyl ester group]-2-hydroxyethyl ammonium methyl sulfate. The mixture was stirred for 15 minutes and CaCl was added₂. Then, 0.5 to 2% by weight of the composition according to the invention of example 2, relative to the total weight of the softener, is added. The mixture was stirred for 15 minutes and cooled to room temperature with stirring (viscosity measurement: results are35+/-5 mPas. (shear rate 106 sec-1)).

Example 5

Preparation of a clear homogeneous shampoo comprising the composition of the invention

Table 3: composition of transparent homogeneous shampoo formulation

1) Ucare Polymer JR-400, source: noveon

2) The source is as follows: schweizerhall

3) Glydant, source: lonza

4) Texapon NSO IS, source: cognis

5) Tego Betain F50, source: evonik

6) Amphotensid GB 2009, source: zschimmer & Schwarz

7) Monomuls 90L-12, source: gruenau

8) Sodium paraben, source: NIPA

The shampoo is prepared by dispersing polyquaternium-10 in water. The remaining ingredients of phase a were added one by one while mixing thoroughly after each adjuvant was added. This premix was added to the polyquaternium-10 dispersion and mixed for an additional 5 minutes. Then, premix phase B and premix phase C were added while stirring (Monomuls 90L-12 was heated to melt in Texapon NSO IS). Add phase D and phase E while stirring. Adjusting the pH with citric acid solution until pH: 5.5-6.0, and preparing the shampoo formula without perfuming.

Perfumed shampoos were prepared by adding 0.4 to 0.8 wt.%, relative to the total weight of the shampoo, of the composition of the invention of example 2 to the unperfumed shampoo formulation of table 3 under gentle shaking.

Example 6

Preparation of a structured body wash comprising the composition of the invention

Table 4: composition of shower gel formula

Composition (I)	Amount (% by weight)
		Deionized water	49.350
Tetrasodium EDTA¹⁾	0.050
		Acrylate copolymer²⁾	6.000
Sodium C12-C15 alkanolpolyether sulfate³⁾	35.000
		20% aqueous solution of sodium hydroxide	1.000
Cocoamidopropyl betaine⁴⁾	8.000
		Methylchloroisothiazolinone and methylisothiazolinone⁵⁾	0.100
Citric acid (40%)	0.500

1) An EDETA B powder; trade mark and origin: BASF

2) CARBOPOL AQUA SF-1 polymer; trade mark and origin: NOVEON

3) ZETESOL AO 328U; trade mark and origin: ZSCHEMMER & SCHWARZ

4) TEGO-BETAIN F50; trade mark and origin: GOLDSCHMIDT

5) KATHON CG; trade mark and origin: ROHM & HASS

A body wash was prepared by adding 0.5 to 1.5 wt% of the inventive composition of example 2 to the unperfumed body wash formulation of table 4 under gentle shaking.

Example 7

Preparation of clear shower gel comprising the composition of the invention

Table 5: composition of transparent shower gel formula

Composition (I)	Concentration (% by weight)
		Deionized water	52.40
Tetrasodium EDTA¹⁾	0.10
		Sodium benzoate	0.50
Propylene glycol	2.00
		Sodium C12-C15 alkanolpolyether sulfate²⁾	35.00
Cocoamidopropyl betaine³⁾	8.00
		Polyquaternium-7⁴⁾	0.20
Citric acid (40%)	1.00
		Sodium chloride	0.80

1) An EDETA B powder; trade mark and origin: BASF

2) ZETESOL AO 328U; trade mark and origin: ZSCHEMMER & SCHWARZ

3) TEGO-BETAIN F50; trade mark and origin: GOLDSCHMIDT

4) Merquatt 550; trade mark and origin: LUBRIZOL

A clear body wash was prepared by adding 0.5 to 1.5 wt% of the inventive composition of example 2 to the unperfumed body wash formulation of table 5 under gentle shaking.

Example 8

Preparation of a milky body wash comprising the composition of the invention

Table 6: composition of milky body wash formula

Composition (I)	Concentration (% by weight)
		Deionized water	50.950
Tetrasodium EDTA¹⁾	0.050
		Sodium benzoate	0.500
Glycerol 86 percent	3.500
		Sodium dodecyl polyoxyethylether sulphate²⁾	27.000
Polyquaternium-7³⁾	1.000
		Cocoamidopropyl Betaine (Coco-Betaine)⁴⁾	6.000
PEG-120 methyl glucose trioleate⁵⁾	1.000
		Citric acid (40%)	1.000
Ethylene glycol distearate&Laureth-4&Cocoamidopropyl betaine⁶⁾	3.000
		20 percent of sodium chloride	5.000
PEG-40 hydrogenated Castor oil⁷⁾	1.000

1) An EDETA B powder; trade mark and origin: BASF

2) Texapon NSO IS; trade mark and origin: COGNIS

3) Merquatt 550; trade mark and origin: LUBRIZOL

4) DEHYTON AB-30; trade mark and origin: COGNIS

5) Glucamine LT; trade mark and origin: LUBRIZOL

6) EUPERLAN PK 3000 AM; trade mark and origin: COGNIS

7) CREMOPHOR RH 40; trade mark and origin: BASF

A clear body wash was prepared by adding 0.5 to 1.5 wt% of the inventive composition of example 2 to the unperfumed body wash formulation of table 6 under gentle shaking.

Example 9

Preparation of a pearlescent shampoo comprising the composition of the invention

Table 7: composition of pearly luster homogeneous shampoo formula

1) EDETA B powder, source: BASF

2) Jaguar C14S, source: rhodia

3) Ucare Polymer JR-400, source: noveon

4) Sulfetal LA B-E, source: zschimmer & Schwarz

5) Zetesol LA, source: zschimmer & Schwarz

6) Tego Betain F50, source: evonik

7) Xiameter MEM-1691, source: dow Corning

8) Lanete 16, source: BASF

9) Complerlan 100, source: cognis

10) Cutina AGS, source: cognis

11) Kathon CG, source: rohm & Haas

12) D-panthenol, source: roche

The shampoo was prepared by dispersing guar hydroxypropyltrimonium chloride and polyquaternium-10 in water and tetrasodium EDTA. Once phase a was homogeneous, NaOH 10% solution (phase B) was added. Then, add pre-mixed phase C. And the mixture was heated to 75 ℃. Add phase D ingredients and mix until uniform. The mixture was cooled. Phase E ingredients were added with mixing at 45 ℃. The final viscosity was adjusted with 25% NaCl solution and the pH was adjusted to 5.5-6 with 10% NaOH solution.

A perfumed pearlescent shampoo was prepared by adding 0.4 to 0.8 wt% of the inventive composition of example 2 to the unflavored shampoo formulation of table 7 under gentle shaking to the total weight of the shampoo.

Example 10

Table 8: composition of milky body wash formula

6) An EDETA B powder; trade mark and origin: BASF

7) CARBOPOL AQUA SF-1 polymer; trade mark and origin: NOVEON

8) ZETESOL AO 328U; trade mark and origin: ZSCHEMMER & SCHWARZ

9) TEGO-BETAIN F50; trade mark and origin: GOLDSCHMIDT

10) KATHON CG; trade mark and origin: ROHM & HASS

A clear body wash was prepared by adding 0.5 to 1.5 wt% of the inventive composition of example 2 to the unperfumed body wash formulation of table 8 under gentle shaking.

Example 11

Preparation of eau de toilette comprising the Compound of the invention

The eau de toilette was prepared by adding 5 to 20% by weight of the composition of the invention of example 2, relative to the total weight of the eau de toilette, to ethanol under gentle shaking.

Claims

1. Use as perfuming ingredient of a compound of formula (I):

n represents 1 or 2.

2. Use according to claim 1, characterized in that n represents 1.

3. A method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least one compound of formula (I):

n represents 1 or 2.

4. A method according to claim 3, characterised in that n represents 1.

5. A perfuming composition comprising:

i) at least one compound of formula (I) as defined in any one of claims 1 to 4;

iv) optionally, at least one flavor adjuvant.

6. A perfumed consumer product comprising at least one compound of formula (I) as defined in any one of claims 1 to 4 or a composition as defined in claim 5.

7. A perfumed consumer product according to claim 6, characterized in that the consumer product base is a perfume, a fabric care product, a body-care product, an air care product or a home care product.

8. A perfumed consumer product according to claim 7, characterized in that the consumer product base is a fine perfume, a paint-on perfume or eau de toilette, a cologne, a shaving or after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain care product, a shampoo, a coloring preparation, a colour care product, a hair styling product, a dental care product, a disinfectant, an intimate care product, a hair spray, a vanishing cream, a body balm or antiperspirant, a depilatory, a tanning or sunscreen product, a nail product, a skin cleanser, a cosmetic product, a perfumed soap, a bath mousse, a bath oil or gel, or a foot/hand care product, a hygiene product, an air freshener, a "ready to use" powdered air freshener, a mould remover, a furniture care product, a wipe, a dish detergent or hard-surface detergent, Leather care products, automotive care products.